Production of 5-methylene-2,4-oxazolidinediones

ABSTRACT

THE PRODUCTION OF 5-METHYLENE-2,4-OXAZOLIDINEDIONES BY CYCLIZATION OF B-AMINOLACTAMIDEURETHANES AT ELEVATED TEMPERATURE, AND THE NEW 5-METHYLENE-2,4-OXAZOLIDINEDIONES. THE NEW COMPOUNDS WHICH CAN BE PREPARED BY THE PROCESS ACCORDING TO THE INVENTION ARE FUNGICIDES AND VALUABLE STARTING MATERIALS FOR THE PRODUCTION OF DYES AND PESTICIDES.

United States Patent 3,709,895 PRODUCTION OF S-METHYLENE-2,4-0XAZOLIDINEDIONES Reinhold Kohlhaupt, Frankenthal, and FriedrichBecke, Heidelberg, Germany, assignors to Badische Anilin- & Soda-FabrikAktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. FiledSept. 16, 1970, Ser. No. 72,867 Claims priority, application Germany,Sept. 18, 1969, P 19 47 193.3 Int. Cl. C07d 85/34 US. Cl. 260-307 B 9Claims ABSTRACT OF THE DISCLOSURE The production of-methylene-2,4-oxazolidinediones by cyclization ofB-aminolactamideurethanes at elevated temperature, and the new5-methylene-2,4-oxazolidinediones. The new compounds which can beprepared by the process according to the invention are fungicides andvaluable starting materials for the production of dyes and pesticides.

The invention relates to a process for the production of5-methylene-2,4-oxazolidinediones by cyclization 'ofB-aminolactamideurethanes at elevated temperatures. The invention alsorelates to new substances of this type.

It is known that choralcyanohydrinphenylurethane can be converted byheating with acid into S-dichloromethybene-3-phenyl-2,4-oxazolidinedione (Journal Chem. Soc. 1940, 1512). Theproduction of the 5-methylene-2,4-ox azolidinediones bearing nosubstituents on the methylene radical has not hitherto been described.

One object of this invention is a new process for the production ofnew-5-me'thylene-2,4-oxazolidinediones in good yields and high purity.

Another object of this invention is the new S-methylene-2,4oxazolidinediones these and other objects are achieved and5-methylene-2,4-oxazolidinediones having the general Formula I:

where R denotes an aliphatic, cycloaliphatic, araliphatic or aromaticradical, are obtained advantageously by cyclizing, at a temperature offrom 100 to 200 C., a ,B-aminolactamideurethane having the generalFormula II:

R: R2I\'I-CH2CHC ONHa (|3-NHR (I where R has the meanings given aboveand the individual radicals R may be identical or different and eachdenotes an aliphatic or cycloaliphatic radical, at a temperature of from100 to 200 C.

When 5 dimethylaminolactamidemethylurethane is used, the reaction may berepresented by the following equation:

3,709,895 Patented Jan. 9, 1973 The process according to the inventionyields a large number of new 5-methylene-2,4-oxazolidinediones in asimple Way and in good yields and high purity.

The starting materials (II) may be prepared by reaction of appropriateB-aminolactamides with isocyanates. Preferred starting materials (II)and consequently preferred end products (I) are those in which R denotesan alkyl radical having 1 to 8 carbon atoms, alkenyl radical having 2 to8 carbon atoms, a cycloalkyl radical having 5 or 6 carbon atoms, anaralkyl radical having 7 to 12 carbon atoms or a phenyl radical, and theindividual radicals R may be identical or different and each denotes analkyl radical having 1 to 8 carbon atoms or a cycloalkyl radical having5 to 6 carbon atoms.

The following are examples of suitable starting materials (II):

fi-dimethylaminolactamide-N-methylurethane,

p-diethylaminolactamide-N'-methylurethane,,6-dicyclohexylaminolactamide-N'-methylurethane andp-methylethylaminolactamide-N'-methylurethane and also the correspondingN'-n-butylurethanes, N-p-chlorophenylurethanes, N-n-octylurethanes,N-cyclopentylurethanes and 40 N-benzylurethanes.

The reaction is carried out at a temperature of from to 200 0.,preferably from to C. at atmospheric, superatmospheric or preferablysubatmospheric pressure, continuously or batchwise. Advantageously, apressure of less than 50 mm. is used. If desired solvents which areinert under the reaction conditions may be used such as water; acidamides bearing two substituents on the nitrogen atom such asN-methylpyrrolidone, dimethyl formamide; ethers such as ethylene glycoldimethyl ether, diethyl ether; dimethyl sulfoxide; or appropriatemixtures, advantageously of water and one of the abovementioned organicsolvents.

The reaction may be carried out as follows: The starting material, withor without a solvent, is kept for one to four hours at the reactiontemperature. The end of the reaction can be detected as a rule by thefact that elimination of amine or ammonia can no longer be observed. Theend product is isolated from the reaction mixture by a conventionalmethod, for example by fractional distillation with or withoutrecrystallization of the distillation residue. An advantageousembodiment consists in carrying out the reaction in a vacuumdistillation vessel, the S-methylene-Z,4-oxazolidinedione beingdistilled off as it is formed. The eliminated amine may be condensed andused again for the production of starting material (II).

The new compounds which may be prepared according to the invention arevaluable fungicides and valuable starting materials for the productionof dyes and pesticides. Thus for example3-methyl-5-methylene-2,4-oxazolidinedione used in a concentration ofonly 10 p.p.m. or 3-butyl-5-methylene-2,4-oxazolidinedione used inconcentration of only 25 ppm. have a good fungicidal action onAspergillus niger.

The invention is illustrated by the following examples in which theparts referred to are parts by weight.

EXAMPLE 1 S-methylene-3 -methyl-2,4-oxazolidinedione (a) In a stirredvessel with vacuum distillation 189.3 parts ofdimethylaminolacetamidemethylurethane is heated at 30 mm. over a periodof thirty minutes up to 130 to 140 C.; thermal reaction of the urethaneand distillation of the end product formed begin at about 120 C. Afteran hour, the reaction is over. The distillate begins to solidify duringdistillation, 92.5 parts (74.4% of the theory) ofS-methylene-3-methyl-2,4-oxazolidinedione having a melting point of from80 to 81 C. is obtained.

(b) 273.4 parts of fi-dibutylaminolactamidemethylurethane is dissolvedin 1000 parts of N-methylpyrrolidone. The solution obtained is 'heatedfor two hours at 140 C. Elimination of dibutylamine and ammonia is thencomplete.

After the solvent has been distilled off in vacuo, the distillationresidue is recrystallized from methanol. 79.4 parts (62.3% of thetheory) of 5-methylene-3-methyl- 2,4-oxazolidinedione is obtained havinga melting point of from 80 to 81 C.

EXAMPLE 2 5-methylene-3- (n-butyl -2,4-oxazolidinedione 259.3 parts ofB-diethylaminolactamide-mbutylurethane is thermally treated as describedin Example 1(a). 132.5 parts of crude end product distils o ver.

Redistillation gives 101.1 parts (60.4% of the theory) of5-methylene-3-(n-butyl)-2,4-oxazolidinedione having a boiling point of81 to 83 C. at 1 mm. a 1.4762.

EXAMPLE 3 S-methylene-3-cyclohexyl-2,4-oxazolidinedione 285.4 parts of5-diethylaminolactamidecyclohexylurethane is heated at 150 C. for ninetyminutes as described in Example 1(a). 166.8 parts of crude end productdistils over. After fractionation, 1360.6 parts (69.7% of the theory) ofS-methyleue-Bcyclohexyl-2,4-oxazolidinedione is chained having a meltingpoint of l300 to 135 C. at 2 mm.

EXAMPLE 4 S-methylene-3-allyl-2,4-oxazolidinedione 243.1 parts of,S-diethylaminolactamideallylurethane is thermally treated as describedin Example 1(a). 121.5 parts of crude end product distils over. Byfractionation, 95.3 parts (62.2% of the theory) of 5-methylene-3-allyl-2,4-oxazolidinedione is obtained having a boiling point of 72 to 74 C n1.4962.

EXAMPLE 5 5-methylene-3-(p-chlorophenyl)-2,4-oxazolidinedione 313.8parts of B-diethylaminolactarnide-p-chlorophenylurethane is heated forninety minutes at 160 C. as de- (I) where R denoes alkyl of l to 8carbon atoms, alkenyl of 2 to 8 carbon atoms, cycloalkyl of 5 or 6carbon atoms, benzyl or phenyl, which comprises cyclizing at atemperature. of from to 200 C. a p aminolactamideurethane having theformula:

R I IU-N-CHg-CH-C ONH:

{J-NH-R Where R has the meanings given above and the individual radicalsR may be identical or different and each denotes alkyl of 1 to 8 carbonatoms or cycloalkyl of 5 to 6 carbon atoms.

2. A process as claimed in claim 1 wherein cyclization is carried out atfrom to C.

3. A process as claimed in claim 1 wherein cyclization is carried out ata pressure of less than 50 mm.

4. A process as claimed in claim 1 wherein cyclization is carried out inthe presence of an inert solvent.

5. A 5-methylene-2,4-oxazolidinedione having the formula:

CLIPS-(3:0

where R denotes alkyl of 1- to 8 carbon atoms, alkenyl of 2 to 8 carbonatoms, cycloalkyl of S or 6 carbon atoms, benzyl or phenyl. I

6. An oxazolidinedione as claimed in claim 5 wherein R is alkyl of l to8 carbon atoms.

7. n oxazolidinedione as claimed in claim 5 wherein R is allyl.

8. An oxazolidinedioue as claimed in claim 5 wherein R is cyclohexyl.

9. A 5-methylene-2,4-oxazolidinedione having the formula:

CHz=O-C=O where R is chlorophenyl.

References Cited UNITED STATES PATENTS 3,280,136 10/1966 Finkbeiner260-299 ALTON D. ROLLINS, Primary Examiner R. V. RUSH, AssistantExaminer US. Cl. X.R. 424272

